EP2933296A1 - Fluorescent reactive dyes, process for the production thereof and their use - Google Patents

Fluorescent reactive dyes, process for the production thereof and their use Download PDF

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Publication number
EP2933296A1
EP2933296A1 EP14165125.7A EP14165125A EP2933296A1 EP 2933296 A1 EP2933296 A1 EP 2933296A1 EP 14165125 A EP14165125 A EP 14165125A EP 2933296 A1 EP2933296 A1 EP 2933296A1
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EP
European Patent Office
Prior art keywords
alkyl
hydrogen
aryl
alkoxy
halogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP14165125.7A
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German (de)
English (en)
French (fr)
Inventor
Yongnian Dr. Gao
Clemens Dr. Grund
Ulrich Hanxleden
Manfred Dr. Hoppe
Michael Dr. Sting-Rosen
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Dystar Colours Distribution GmbH
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Dystar Colours Distribution GmbH
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Publication date
Application filed by Dystar Colours Distribution GmbH filed Critical Dystar Colours Distribution GmbH
Priority to EP14165125.7A priority Critical patent/EP2933296A1/en
Priority to TW104111103A priority patent/TWI597327B/zh
Priority to JP2016562583A priority patent/JP6483726B2/ja
Priority to US15/106,999 priority patent/US10227491B2/en
Priority to MA39387A priority patent/MA39387B1/fr
Priority to PCT/EP2015/057542 priority patent/WO2015158574A1/en
Priority to MX2016013586A priority patent/MX2016013586A/es
Priority to EP15715232.3A priority patent/EP3131974B1/en
Priority to CN201580019747.4A priority patent/CN106459603B/zh
Priority to ES15715232.3T priority patent/ES2663845T3/es
Priority to PT157152323T priority patent/PT3131974T/pt
Publication of EP2933296A1 publication Critical patent/EP2933296A1/en
Priority to SV2016005302A priority patent/SV2016005302A/es
Withdrawn legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00Diaryl- or thriarylmethane dyes
    • C09B11/04Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10Amino derivatives of triarylmethanes
    • C09B11/24Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/02Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
    • C09B62/021Specific dyes not provided for in groups C09B62/024 - C09B62/038
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/02Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
    • C09B62/04Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/4401Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system
    • C09B62/4403Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system the heterocyclic system being a triazine ring
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/4401Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system
    • C09B62/4422Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system the heterocyclic system being a pyrimidine ring
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/503Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/02Printing inks
    • C09D11/03Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/38General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
    • D06P1/382General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes reactive group directly attached to heterocyclic group
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58Material containing hydroxyl groups
    • D06P3/60Natural or regenerated cellulose

Definitions

  • the present invention relates to the technical field of reactive dyestuffs for dyeing and printing of hydroxyl-, amino- and/or carboxamido-containing material.
  • Fluorescent reactive dyes are known from prior art and can be used as colorants in different applications, see for example DE 2337488 , EP 153480 , DE 2442839 and DE 1955849 .
  • the present invention is thus directed to a dye of formula (I) wherein in each case independent from each other W is O, S or NH, R 1 and R 2 is hydrogen, alkyl, alkyl substituted by one or more substituents selected from the group consisting of methoxy, hydroxy, sulfato, sulfo and chloro, aryl, aryl substituted by one or more substituents selected from the group consisting of chloro, acetylamino, sulfo, hydroxy, carboxy, (C 1 -C 4 )-alkanoyl, (C 1 -C 4 )-alkoxy and (C 1 -C 4 )-alkyl or benzyl, R 3 and R 4 is hydrogen, alkyl, hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, N-cinnamoylamino, halogen, cyano, SO 3 M, COOM, nitro,
  • the chromophore in this invention is a group having the following structure:
  • a group removable under alkaline conditions is a group which will leave the molecule under alkaline conditions to yield a vinyl sulfone.
  • Non-limiting examples of such groups are OSO 3 M, SSO 3 M, OCOCH 3 , OPO 3 M and halogen.
  • the anion is defined by the production and/or purification process.
  • Non-limiting examples of anions are halogen, sulfates, benzolsulfonates, toluolsulfonates, tetraborofluorates or acetates.
  • Preferred are chloride, bromide and sulfates.
  • a spacer is a group that can react on one side with the chromophore / chromophore precursor and with a second reaction center of the molecule with a reactive anchor.
  • a spacer can be aliphatic-, aromatic- or mixed aliphatic/aromatic.
  • Non-limiting examples are substituted- or unsubstituted-alkylen-diamines for aliphatic-spacers, substituted- or unsubstituted-aniline-/naphthaline-diamines for aromatic-spacers and aminoalkyl substituted anilines-/naphthalines- for mixed aliphatic/aromatic-spacers.
  • a reactive anchor is a group that is directly fixed with a covalent bond to the chromophor or via a spacer that can form a covalent bond to hydroxyl-, amino- and/or carboxamido-containing fibre. This can be achieved with groups having activated leaving groups, such as halogen or OSO 3 H, which can be replaced in a nucleophilic substitution reaction by the hydroxyl-, amino-and/or carboxamido-containing fibre.
  • Non-limiting examples are: 2,4,6-trifluoro-5-chloropyrimidine (FCP), 2,4,6-trifluoro-pyrimidine (TFP), 2,4,6-trifluoro-1,3,5-triazine (TFT), 2,4,6-trilchloro-1,3,5-triazine (Cyanuric chloride), ß-chloroethylsulfonyl-groups, 2,3-dibromo-propionic acid derivatives (CO-CHBr-CH 2 Br) and ß-sulfatoethylsulfonyl groups and 2,3-dichloro-quinoxaline.
  • FCP 2,4,6-trifluoro-5-chloropyrimidine
  • TFT 2,4,6-trifluoro-1,3,5-triazine
  • Cyanuric chloride ß-chloroethylsulfonyl-groups, 2,3-dibromo-propionic acid derivatives
  • a second reaction type to form a covalent bond to hydroxyl-, amino- and/or carboxamido-containing material is the nucleophilic addition to an activated carbon-carbon double bond by the hydroxyl-, amino- groups of the fibre.
  • the invention is directed to a dye as described above, wherein in each case independent from each other W is O, S or NH, R 1 and R 2 is hydrogen, alkyl, alkyl substituted by one or more substituents selected from the group consisting of methoxy, hydroxy, sulfato, sulfo and chloro, aryl, aryl substituted by one or more substituents selected from the group consisting of chloro, acetylamino, sulfo, hydroxy, carboxy, (C 1 -C 4 )-alkanoyl, (C 1 -C 4 )-alkoxy and (C 1 -C 4 )-alkyl or benzyl, R 3 and R 4 is hydrogen, alkyl, hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, N-cinnamoylamino, halogen, cyano, SO 3 M, COOM, nitro, acyl
  • This invention refers to all kinds of tautomeric and geometric isomers of the dyes of the formula (I).
  • Alkyl groups in this invention may be straight-chain or branched and are (C 1 -C 12 )-alkyl groups, preferably (C 1 -C 8 )-alkyl groups, for example n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, sec-butyl, tert-butyl and methylbutyl.
  • alkoxy groups which accordingly are preferably (C 1 -C 8 )-alkoxy, for example methoxy and ethoxy
  • thioalkoxy groups which are preferably (C 1 -C 8 )-thioalkoxy, for example - SCH 3 and -SC 2 H 5 .
  • Cycloalkyl groups are preferably (C 3 -C 8 )-cycloalkyl. Particularly preferred are cyclopentyl and cyclohexyl.
  • the term cyloalkyl comprises for the purpose of the present invention substituted cycloalklyl groups and unsatured cycloalkyl groups as well. A preferred group of this type is cyclopentenyl.
  • Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, acyl, cyano, nitro, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis-(hydroxyalkyl)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy.
  • Aryl groups appearing in this invention are preferably phenyl or naphthyl.
  • the terms phenyl and naphthyl comprise unsubstituted as well as substituted phenyl and naphthyl.
  • Preferred substituents are alkyl, cycloalkyl, heterocycloalkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis-(hydroxyalkyl)amino, monoalkyl-mono-(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy.
  • Heteroaryl groups appearing in this invention are preferably pyridine, pyrimidine, pyridazine, pyrazine, pyrrole, imidazole, pyrazole, 1,2,4-thiadiazole, 1,2,4-triazole, tetrazole, thiophene, thiazole, isothiazole, benzothiazole, benzoisothiazole, 1,3,4-thiadiazole, furane, oxazole, benzoxazole or isoxazole.
  • heteroaryl comprises the above groups in unsubstituted as well as in substituted form.
  • Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis- (hydroxyalkyl)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy.
  • Heterocycloalkyl groups are preferably pyrrolidine, piperidine, morpholine, tetrahydrofuran or piperazine.
  • the term heterocycloalkyl comprises the above groups in unsubstituted as well as in substituted form.
  • Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis-(hydroxylalkyl)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, aminocarbonylamino, aminosulfonylamino, alkoxycarbonyl and acyloxy.
  • Halogen is preferably chlorine, bromine or fluorine.
  • M is preferably hydrogen, lithium, sodium or potassium.
  • R 1 and R 2 is hydrogen, alkyl, alkyl substituted by one or more substituents selected from the group consisting of methoxy, hydroxy, sulfato, sulfo and chloro, aryl, aryl substituted by one or more substituents selected from the group consisting of chloro, acetylamino, sulfo, hydroxy, carboxy, (C 1 -C 4 )-alkanoyl, (C 1 -C 4 )-alkoxy and (C 1 -C 4 )-alkyl or benzyl, R 3 and R 4 is hydrogen, alkyl, hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, N-cinnamoylamino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thio
  • R 1 and R 2 is hydrogen, alkyl, alkyl substituted by one or more substituents selected from the group consisting of methoxy, hydroxy, sulfato, sulfo and chloro, aryl, aryl substituted by one or more substituents selected from the group consisting of chloro, acetylamino, sulfo, hydroxy, carboxy, (C 1 -C 2 )-alkanoyl, (C 1 -C 2 )-alkoxy and (C 1 -C 2 )-alkyl or benzyl, R 3 and R 4 is hydrogen, (C 1 -C 4 )-alkyl, hydroxy, aryl, (C 1 -C 4 )-alkoxy, N-acylamino, halogen, SO 3 M, COOM, acyl, (C 1 -C 4 )-alkylsulfon
  • R 1 and R 2 is hydrogen, (C 1 -C 4 )-alkyl, aryl or benzyl
  • R 3 and R 4 is hydrogen, (C 1 -C 2 )-alkyl, halogen, SO 3 M, COOM or SO 2 -X, wherein X is vinyl or CH 2 CH 2 -Y, wherein Y is a group removable under alkaline conditions
  • Z - is selected from the group consisting of halogen, sulfate, alkylsulfonate, benzolsulfonate, toluolsulfonate, tetraborofluorate and acetate
  • a 1 and A 2 is a spacer of formula (2c-1) or (2d-1) whereby the respective spacer A 1 / A 2 is attached to the chromophore at the * position and to the respective reactive anchor T 1 / T 2 at the ** position, and wherein
  • both reactive anchors T 1 and T 2 are selected from the group of heterocyclic- group-reactive anchors (pyrimidines, triazines) and/or Bromo-propionic acid- derivatives.
  • R 1 and R 2 is hydrogen, alkyl, alkyl substituted by one or more substituents selected from the group consisting of methoxy, hydroxy, sulfato, sulfo and chloro, aryl, aryl substituted by one or more substituents selected from the group consisting of chloro, acetylamino, sulfo, hydroxy, carboxy, (C 1 -C 4 )-alkanoyl, (C 1 -C 4 )-alkoxy and (C 1 -C 4 )-alkyl or benzyl, R 3 and R 4 is hydrogen, alkyl, hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, N-cinnamoylamino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thio
  • R 1 and R 2 is hydrogen, alkyl, alkyl substituted by one substituents selected from the group consisting of methoxy, hydroxy, sulfato, sulfo and chloro, aryl, aryl substituted by one or more substituents selected from the group consisting of chloro, acetylamino, sulfo, hydroxy, carboxy, (C 1 -C 2 )-alkanoyl, (C 1 -C 2 )-alkoxy and (C 1 -C 2 )-alkyl or benzyl, R 3 and R 4 is hydrogen, (C 1 -C 4 )-alkyl, hydroxy, aryl, (C 1 -C 4 )-alkoxy, N-acylamino, halogen, SO 3 M, COOM, acyl, (C 1 -C 4 )-alkylsulfonyl
  • R 1 and R 2 is hydrogen, (C 1 -C 4 )-alkyl, aryl or benzyl
  • R 3 and R 4 is hydrogen, (C 1 -C 2 )-alkyl, halogen, SO 3 M, COOM or SO 2 -X, wherein X is vinyl or CH 2 CH 2 -Y, wherein Y is a group removable under alkaline conditions
  • Z - is selected from the group consisting of halogen, sulfate, alkylsulfonate, benzolsulfonate, toluolsulfonate, tetraborofluorate and acetate
  • a 1 and A 2 is a spacer of formula (2a), (2b-1) or (2e-1) whereby the respective spacer A 1 / A 2 is attached to the chromophore at the * position and to the respective reactive anchor T 1 / T 2 at the ** position and where
  • R 1 and R 2 is hydrogen, alkyl, alkyl substituted by one or more substituents selected from the group consisting of methoxy, hydroxy, sulfato, sulfo and chloro, aryl, aryl substituted by one or more substituents selected from the group consisting of chloro, acetylamino, sulfo, hydroxy, carboxy, (C 1 -C 4 )-alkanoyl, (C 1 -C 4 )-alkoxy and (C 1 -C 4 )-alkyl or benzyl, R 3 and R 4 is hydrogen, alkyl, hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, N-cinnamoylamino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thio
  • a 2 is a reactive anchor of formula (2c) or (2d) whereby the spacer A 2 is attached to the chromophore at the * position and to the reactive anchor T 2 at the ** position, and wherein d is 1 to 4, e is 0 to 3, f is 0 to 3, g is 0 to 3, Q is O, NH or S, R 6 is hydrogen, halogen, alkyl, N-acylamino, alkoxy, thioalkoxy, hydroxy, alkoxycarbonyl, acyl, arylol, acyloxy, aryloyloxy, cycloalkyl, aryl, SO 3 M or COOM, R 8 and R 9 is hydrogen, alkyl, alkoxy, aryl, hydroxyl, NH-CH 2 -CH 2 -OSO 3 H, SO 3 M or COOM, T 2 is SO 2 -X, wherein X is vinyl or CH 2 CH 2 -Y, wherein Y is a group removable under alkaline
  • R 1 and R 2 is hydrogen, alkyl, alkyl substituted by one substituents selected from the group consisting of methoxy, hydroxy, sulfato, sulfo and chloro, aryl, aryl substituted by one or more substituents selected from the group consisting of chloro, acetylamino, sulfo, hydroxy, carboxy, C 1 -C 2 -alkanoyl, C 1 -C 2 -alkoxy and C 1 -C 2 -alkyl or benzyl, R 3 and R 4 is hydrogen, (C 1 -C 4 )-alkyl, hydroxy, aryl, (C 1 -C 4 )-alkoxy, N-acylamino, halogen, SO 3 M, COOM, acyl, (C 1 -C 4 )-alkylsulfonyl, (C 1 -
  • R 1 and R 2 is hydrogen, (C 1 -C 4 )-alkyl, aryl, aryl or benzyl
  • R 3 and R 4 is hydrogen, (C 1 -C 2 )-alkyl, halogen, SO 3 M, COOM or SO 2 -X, wherein X is vinyl or CH 2 CH 2 -Y, wherein Y is a group removable under alkaline conditions
  • Z - is selected from the group consisting of halogen, sulfate, alkylsulfonate, benzolsulfonate, toluolsulfonate, tetraborofluorate and acetate
  • a 1 is a spacer of formula (2a), (2b-1) or (2e-1) whereby the spacer A 1 is attached to the chromophore at the * position and to the reactive anchor T 1 at the ** position and wherein c is 1 to 3, f is
  • the dyes of the present invention can be produced in different ways.
  • the invention is also directed to two processes for the production of the inventive dyes.
  • a process for the production of dyes as described above comprising the steps of:
  • the end product, which contains ⁇ -sulfatoethylsulfonyl-groups can optionally also be subjected to a vinylization reaction.
  • a vinylizable reaction group such as ⁇ -sulfatoethylsulfonyl is converted into its vinyl form.
  • Such reactions are known to a person skilled in the art. They are generally performed in a neutral to alkaline medium at a temperature, for example, from 20 to 80 °C, at a pH of, for example, from 7 to 10.
  • the dyes of formula (I) are fiber-reactive, i.e. are containing fiber-reactive functional rests.
  • Fiber-reactive functional rests refer to rests capable of reacting with the hydroxyl groups of cellulosic materials, the amino, carboxyl, hydroxyl and thiol groups in the case of wool and silk, or with the amino and possibly carboxyl groups of synthetic polyamides to form covalent chemical bonds.
  • the dyes of the present invention are suitable for dyeing and printing of natural, manufactured,regenerated, mechanically or chemically modified, recycled or synthetic hydroxyl-, amino-, and/or carboxamido-containing fiber materials and their blends by the application methods numerously described in the art for reactive dyes.
  • natural fibre materials are vegetable fibres such as seed fibres i.e. cotton, organic cotton, kapok, coir from coconut husk; bast fibers i.e. flax, hemp, jute, kenaf, ramie, rattan; leaf fibres i.e. sisal, henequen, banana; stalk fibres i.e. bamboo; and fibres from animals such as wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre as well as fur and leather materials.
  • seed fibres i.e. cotton, organic cotton, kapok, coir from coconut husk
  • bast fibers i.e. flax, hemp, jute, kenaf, ramie, rattan
  • leaf fibres i.e. sisal, henequen, banana
  • stalk fibres i.e. bamboo
  • fibres from animals such as wool, organic wool, silk, cashmere wool, alpaca
  • manufactured and regenerated fibres are cellulosic fibres such as paper and cellulosic regenerated fibres such as viscose rayon fibres, acetate and triacetate fibers and Lyocell fibers.
  • nylon materials like nylon-6, nylon-6.6 and aramid fibres.
  • the above-mentioned substrates to be dyed can be present in various forms such as but not limited to yarn, woven fabric, loop-formingly knitted fabric or carpet.
  • Fiber and blends containing such fiber selected from the group consisting of: synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 and aramid fibres, vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres, sisal, henequen, banana; stalk fibres, bamboo; fibres from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre as well as fur and leather materials; manufactured, regenerated and recycled fibres, cellulosic fibres; paper fibres, cellulosic regenerated fibres, viscose rayon fibres, acetate and triacetate fibers, and Lyocell fibers comprising one or more dye(s) as described above either in chemically and/or physically bound form thus forms another aspect of the present invention.
  • the dyes of the present invention and their salts or mixtures can be used as a single dyeing product in dyeing or printing processes or it can be part of a di/tri or multi-component combination product in dyeing or in printing compositions.
  • Dyes of this invention and their salts or mixtures are highly compatible with other known and/or commercially available dyes and they can be used together with such dyes to obtain specific hues of similarly good technical performance.
  • Technical performance includes build-up, fastness properties and levelness.
  • a chemical composition comprising one or more dye(s) of the present invention forms yet another aspect of the present invention.
  • the water solubility of the dyes according to the invention is very good, they can also be used with advantage in customary continuous dyeing processes.
  • the dyes of the present invention can also be used in digital printing processes, in particular in digital textile printing.
  • An aqueous solution for dying comprising one or more chemical compounds as described above forms still another aspect of the present invention.
  • an ink for digital textile printing comprising a dye of the present invention.
  • the inks of the present invention comprise the dye of the present invention in amounts which preferably range from 0.1 % by weight to 50 % by weight, more preferably from 1 % by weight to 30 % by weight and most preferably from 1 % by weight to 15 % by weight, based on the total weight of the ink.
  • the inks, as well as the dyes of the present invention may, if desired, contain further dyes used in digital printing.
  • a conductivity of 0.5 to 25 mS/m can be set by adding an electrolyte.
  • Useful electrolytes include for example lithium nitrate and potassium nitrate.
  • the inks of the present invention may include organic solvents at a total level of 1-50% and preferably 5-30% by weight.
  • Suitable organic solvents are for example alcohols, for example methanol, ethanol, 1-propanol, isopropanol, 1-butanol, tert-butanol, pentyl alcohol, polyhydric alcohols for example: 1,2-ethanediol, 1,2,3-propanetriol, butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-propanediol, 2,3-propanediol, pentanediol, 1,4-pentanediol, 1,5-pentanediol, hexanediol, D,L-1,2-hexanediol, 1,6-hexanediol, 1,2,6-hexanetriol, 1,2-octanediol, polyalkylene glycols, for example: polyethylene glycol, polypropylene glycol, alkylene glycols having 1
  • the inks of the invention may further include customary additives, for example viscosity moderators to set viscosities in the range from 1.5 to 40.0 mPas in a temperature range from 20 to 50 °C.
  • Preferred inks have a viscosity of 1.5 to 20 mPas and particularly preferred inks have a viscosity of 1.5 to 15 mPas.
  • Useful viscosity moderators include rheological additives, for example: polyvinylcaprolactam, polyvinylpyrrolidone and their copolymers polyetherpolyol, associative thickeners, polyurea, polyurethane, sodium alginates, modified galactomannans, polyetherurea, polyurethane, nonionic cellulose ethers.
  • rheological additives for example: polyvinylcaprolactam, polyvinylpyrrolidone and their copolymers polyetherpolyol, associative thickeners, polyurea, polyurethane, sodium alginates, modified galactomannans, polyetherurea, polyurethane, nonionic cellulose ethers.
  • the inks of the invention may include surface-active substances to set surface tensions of 20 to 65 mN/m, which are adapted if necessary as a function of the process used (thermal or piezo technology).
  • Useful surface-active substances include for example all surfactants, preferably nonionic surfactants, butyldiglycol and 1,2-hexanediol.
  • the inks of the present invention may further include customary additives, for example substances to inhibit fungal and bacterial growth in amounts from 0.01 to 1 % by weight based on the total weight of the ink.
  • the inks may be prepared in a conventional manner by mixing the components in water.
  • the inks of the present invention are particularly useful in inkjet printing processes for printing a wide variety of materials, in particular of wool and polyamide fibers.
  • reaction mix was cooled to room temperature and the water was evaporated under reduced pressure delivering 20.5 parts of Intermediate 1 after drying under vacuum conditions.
  • reaction mix was cooled to room temperature and the water was evaporated under reduced pressure delivering 20.5 parts of Intermediate 1 after drying under vacuum conditions.
  • the following amines can be used for 1. Condensation (Amine 1) and for 2. Condensation (Amine 2). After sulfonation and isolation according to example 1 or 2 the following dyes are obtained.
  • the following amines can be used for 1. Condensation (Amine 1) and for 2. Condensation (Amine 2), after sulfonation and isolation according to example 1 or 2 the following dyes are obtained. Amine 1 Amine 2 Expl. Shade on cotton 41 Bluish red 42 Bluish red 43 Bluish red
  • reaction mix was cooled to room temperature and the water was evaporated under reduced pressure delivering 19.8 parts of Intermediate 1 after drying under vacuum conditions.
  • the following amines can be used for the first condensation (Amine 1) and for the second condensation (Amine 2).
  • the following dyes are obtained: Amine 1 Amine 2 Expl. Shade on cotton 138 Red 139 Red 140 Red 141 Red 142 Red 143 Red 144 Bluish red 145 Bluish red 146 Bluish red 147 Bluish red 148 Bluish red 149 Bluish red 150 Bluish red 151 Bluish red 152 Red 153 Red 154 Red 155 Red 156 Violet 157 Violet 158 Violet 159 Bluish red 160 Bluish red 161 Bluish red

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)
  • Luminescent Compositions (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Detergent Compositions (AREA)
EP14165125.7A 2014-04-17 2014-04-17 Fluorescent reactive dyes, process for the production thereof and their use Withdrawn EP2933296A1 (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
EP14165125.7A EP2933296A1 (en) 2014-04-17 2014-04-17 Fluorescent reactive dyes, process for the production thereof and their use
TW104111103A TWI597327B (zh) 2014-04-17 2015-04-07 螢光反應性染料、其生產方法及其用途
PCT/EP2015/057542 WO2015158574A1 (en) 2014-04-17 2015-04-08 Fluorescent reactive dyes, process for the production thereof and their use
US15/106,999 US10227491B2 (en) 2014-04-17 2015-04-08 Fluorescent reactive dyes, process for the production thereof and their use
MA39387A MA39387B1 (fr) 2014-04-17 2015-04-08 Colorants réactifs fluorescents, procédé de production et utilisation de ceux-ci
JP2016562583A JP6483726B2 (ja) 2014-04-17 2015-04-08 蛍光性反応染料、それらを製造するためのプロセス、及びそれらの使用
MX2016013586A MX2016013586A (es) 2014-04-17 2015-04-08 Tinturas reactivas fluorescentes, proceso para su produccion y su uso.
EP15715232.3A EP3131974B1 (en) 2014-04-17 2015-04-08 Fluorescent reactive dyes, process for the production thereof and their use
CN201580019747.4A CN106459603B (zh) 2014-04-17 2015-04-08 荧光活性染料,及其制备方法与应用
ES15715232.3T ES2663845T3 (es) 2014-04-17 2015-04-08 Tintes reactivos fluorescentes, proceso para la producción de estos y su uso
PT157152323T PT3131974T (pt) 2014-04-17 2015-04-08 Corantes reativos fluorescentes, processo para a sua produção e sua utilização
SV2016005302A SV2016005302A (es) 2014-04-17 2016-10-14 Tinturas reactivas fluorescentes, proceso para su producción y su uso

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EP14165125.7A EP2933296A1 (en) 2014-04-17 2014-04-17 Fluorescent reactive dyes, process for the production thereof and their use

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ES (1) ES2663845T3 (es)
MA (1) MA39387B1 (es)
MX (1) MX2016013586A (es)
PT (1) PT3131974T (es)
SV (1) SV2016005302A (es)
TW (1) TWI597327B (es)
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017006940A1 (ja) * 2015-07-09 2017-01-12 富士フイルム株式会社 化合物、着色組成物、インクジェット記録用インク、インクジェット記録方法、インクジェットプリンタカートリッジ、及びインクジェット記録物

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EP2021415B1 (en) 2006-05-18 2017-03-15 Illumina Cambridge Limited Dye compounds and the use of their labelled conjugates
KR102162610B1 (ko) * 2016-08-19 2020-10-07 주식회사 엘지화학 화합물, 이를 포함하는 색재 조성물 및 이를 포함하는 수지 조성물
KR102186097B1 (ko) * 2017-12-26 2020-12-03 주식회사 엘지화학 잔텐계 화합물 및 이를 포함하는 감광성 수지 조성물

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1955849A1 (de) 1969-11-06 1971-05-27 Hoechst Ag Wasserloesliche,reaktive Xanthenfarbstoffe und Verfahren zu ihrer Herstellung
DE2337488B1 (de) 1973-07-24 1975-01-30 Hoechst Ag Verfahren zur Herstellung von reaktiven Xanthenfarbstoffen
DE2442839A1 (de) 1973-09-06 1975-03-13 Ici Ltd Reaktivfarbstoffe
EP0153480A2 (de) 1983-12-28 1985-09-04 Bayer Ag Reaktivfarbstoffe der Diarylaminoxanthen-Reihe, ihre Herstellung und Verwendung
EP0330444A2 (en) * 1988-02-22 1989-08-30 EASTMAN KODAK COMPANY (a New Jersey corporation) Novel thiorhodamines and a novel method of preparation
US20060020141A1 (en) * 2004-07-23 2006-01-26 Xerox Corporation Colorant compounds

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2460491A1 (de) * 1974-12-20 1976-07-01 Hoechst Ag Verfahren zur herstellung von xanthenfarbstoffen
JPH0443536A (ja) * 1990-06-08 1992-02-13 Mitsubishi Kasei Corp 積層体
GB9220964D0 (en) * 1991-11-15 1992-11-18 Ici Plc Anionic compounds
US6843838B2 (en) * 2002-12-31 2005-01-18 Lexmark International, Inc. Inkjet ink, dye set, ink set, and method of use thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1955849A1 (de) 1969-11-06 1971-05-27 Hoechst Ag Wasserloesliche,reaktive Xanthenfarbstoffe und Verfahren zu ihrer Herstellung
DE2337488B1 (de) 1973-07-24 1975-01-30 Hoechst Ag Verfahren zur Herstellung von reaktiven Xanthenfarbstoffen
DE2442839A1 (de) 1973-09-06 1975-03-13 Ici Ltd Reaktivfarbstoffe
EP0153480A2 (de) 1983-12-28 1985-09-04 Bayer Ag Reaktivfarbstoffe der Diarylaminoxanthen-Reihe, ihre Herstellung und Verwendung
EP0330444A2 (en) * 1988-02-22 1989-08-30 EASTMAN KODAK COMPANY (a New Jersey corporation) Novel thiorhodamines and a novel method of preparation
US20060020141A1 (en) * 2004-07-23 2006-01-26 Xerox Corporation Colorant compounds

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017006940A1 (ja) * 2015-07-09 2017-01-12 富士フイルム株式会社 化合物、着色組成物、インクジェット記録用インク、インクジェット記録方法、インクジェットプリンタカートリッジ、及びインクジェット記録物

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JP6483726B2 (ja) 2019-03-13
EP3131974A1 (en) 2017-02-22
TW201544550A (zh) 2015-12-01
EP3131974B1 (en) 2018-01-03
US10227491B2 (en) 2019-03-12
MX2016013586A (es) 2017-02-28
PT3131974T (pt) 2018-03-28
CN106459603B (zh) 2019-08-23
MA39387B1 (fr) 2017-10-31
SV2016005302A (es) 2017-01-23
MA39387A1 (fr) 2016-12-30
TWI597327B (zh) 2017-09-01
JP2017515938A (ja) 2017-06-15
WO2015158574A1 (en) 2015-10-22
US20180194943A1 (en) 2018-07-12
ES2663845T3 (es) 2018-04-17
CN106459603A (zh) 2017-02-22

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